1. PhD Supervisors : Gwénaël Rapenne and Jean-Pierre Launay
Frontiers Workshop Design and Synthesis of a molecular motor incorporating insulating fragments
Guillaume Vives
PhD Supervisors : Gwénaël Rapenne and Jean-Pierre Launay

2. ROTATION OF DECACYCLENE
A non-directional rotor
hexa-tert-butyl decacyclene
Motionless
In rotation
STM Images on Cu (100)
ESQC Calculations

3. PRINCIPLE OF THE ROTARY MOTEUR
(Rotation of one fifth of turn)
Desired behavior
Unwanted mechanism

4. DESIGN
Four Parts :
Stator : Tripodal ligand functionalized to be anchored to the surface.
Rotor : Cp ligand with five rigid arms terminated by electroactive groups (EG)
Insulating Spacers to prevent intramolecular electron transfer.
Joint : Ruthenium atom

5. Stator : Hydrotris(indazolyl)borate ligand
GOAL MOLECULE
Four Parts :
Stator : Hydrotris(indazolyl)borate ligand
Rotor : Substituted Cp terminated by ferrocenyls Insulator : trans Pt(II) complex
Joint : Ruthenium atom

6. INSULATING ROLE OF PLATINUM
- Electrochemical Study 1 2
E1/2(1)
(V/CSE)
E1/2(2)
E1/2
(mV) 1
0,58
0,68
~ 100 2
0,32
0,40
~ 80

7. INSULATING ROLE OF PLATINUM
- Spectoelectrochemical Study 1
Hush formula:
Parametre of electronic coupling :
1 : Vab = 0,036 eV
2 : Vab = 0,025 eV 2

8. INSULATING ROLE OF PLATINUM
DFT (BP86 / 6-31 G**) Geometry optimisation

9. INSULATING ROLE OF PLATINUM
Vab calculation: dimer splitting method
Overlaping between 3d orbital of Fe and the bridging ligand
E3d(Fe)
E(u)
E(g)
E (eV)
Vab (eV) 1
-10,500
-10,767
-10,903
0,136
0,068
-11,000
-11,117
-11,272
0,155
0,077
-11,500
-11,390
-11,649
0,259
0,129 2
-10,849
-10,813
0,036
0,018
-11,231
-11,186
0,045
0,022
-11,522
-11,612
0,090
~ Vab/3 with Pt
Energies of the orbitals and Vab of 1 and 2

10. RETROSYNTHETHIC ANALYSIS

11. SYNTHESIS OF THE RUTHENIUM CENTER

12. SYNTHESIS OF A MODEL MOTOR
Pt fragment synthesis:
Connection

13. CARACTERISATIONS 31P RMN 195Pt {31P} RMN 1H RMN (CD2Cl2) 500 MHz
JPt-P(trans) = 2374 Hz
195Pt {31P} RMN
1H RMN (CD2Cl2) 500 MHz

14. CARACTERISATIONS
Electrochemistry : CV : CH2Cl2, nBu4PF6 0.1 M, 100 mV.s-1
E1/2 (V/SCE) Fe Ru
0.31
0.60
0.52
0.82

15. FUNCTIONALISED STATOR FOR OXIDE SURFACES
Ligand synthesis
Model Ru complex

16. FIRST MOLECULAR MOTOR

17. PERSPECTIVES

18. Groupe NanoSciences (CEMES) LCC
AKNOWLEGMENTS
Groupe NanoSciences (CEMES)
Alexandre Carella
Stéphanie Sistach
Gwénaël Rapenne
Jean Pierre Launay
Christine Viala
LCC
Christine Lepetit
Frontiers Network

19. A biological rotary motor :
ATP SYNTHASE
A biological rotary motor :
The rotation of F1 is controled by the proton gradient through the membrane
J. E. Walker, Angew. Chem. Int. Ed., 1998, 37, 2308

20. SYNTHESIS OF THE ORGANOMETALLIC CORE
KTIB

21. FIRST STRATEGY
Pt fragment synthesis:
Connection: